Separating powdered catalysts from exothermically reactive gases



Oct. 24, 1950 P. w. GARBo SEPARATING Pownmn cA'rALYs'rs FROM ExomERuIcALLY REAC'rIvE GASES Filed Aug. 2, 1945 2 Sheets-'Sheet 1 N www IN VENTOR Oct. 24, 1950 P w GARBQ 2,526,651

SEPARATING F-OWDRD CATALYSTS FRDM EXO'll-IERIIICALLY REACTIVE GASES Filed Aug. 2, 1945 2 Sheets-Sheet 2 N N N I NVENTOR v/Mira Patented Oct. 24, 1950 UNITED STAT SEPARATING POWDERED oA'rALYs'rs FRoM EXoTHEaMIcALLY REACTIVEGASES l Paul W. Garbo, Long Beach, N. Y., assignor Ato Hydrocarbon Research, Inc., New York, N. Y.

Application August 2, 1945, Szerial No. 608,394 y This invention relates toa method for' controlling the temperature of exothermic reactions of gases or vapors carrying entrained catalyst particles after these gaseous reactants have left the reaction zone in which temperature control means 'are incorporated. More particularly it relates to a method for arresting reaction when gaseousreactants flow from a dense bed of fluidized catalyst to the solids disengaging space above the pseudo-liquid level of the fluidized bed.

It is extremely important in exothermic processes to prevent the temperature from rising above the desired level in order to avoid damage to the catalyst and the formation of undesirable products. With strongly exothermic reactions such as the synthesis of hydrocarbons from carbon monoxide and hydrogen, where a xed catalyst bed is employed it is necessary to have every catalyst particle in the immediate' vicinity of, e. g., within a few centimeters, a heat exchange surface in order to avoid local overheating. The fluidized catalyst technique is especially suitable for this type of reaction because the necessity for extensive cooling surfaces or other elaborate and expensive means of obtaining close temperature control is minimized'. Furthermore, unusual uniformity of temperature within the fluidized reaction mass is attained because of the turbulent motion of the catalyst particles and gaseous reactants. I

Difliculty arises, however, from thev lack of effective temperature control once the reactants have left the fluidizeci catalyst mass for which practical cooling means are known. Since the gases emerging from the fluidized dense bed always entrain a certain amount ofthe powdered catalyst and both gases and catalyst are at reaction temperature, the reaction continues to take place between unreacted or incompletely reacted components in contactwith the suspended catalyst particles. Because of the exothermic nature of the reaction, the temperature rises and may reach the point where the character of the products deteriorates markedly and the catalyst is damaged. Such a condition most frequently develops when the emerging gases contain a relatively large proportion of-unreacted components, as when the reaction is carried out in a stepwise manner, and when for some reason local increases occur in the concentration of entrained catalyst, as, for example, within a cyclone separator or where the catalyst collects upon a surface `in contact with the gases. Thus, when a porous refractory elementis used to lter olf powdered iron catalyst from reaction gases containing some 11 Claims. (Cl. 260-449.6)

unreacted hydrogen and carbon monoxide, the layer of catalyst which builds-up on the filter element may easily attain a temperature above f 900 F.; thereby injuring the catalyst and synthesis products. The catalyst layerv may even coke up so that blowing-back is' noteiiective in knocking the catalyst olf from the filter element. Cooling the gases and entrained catalyst sufficiently to stop or materially diminish the exothermic reaction is not feasible in commercialscale operations. Toaecomplish such cooling, the sze and complexity of the reactors would be inordinately increased. For such reasonsordinary heat exchange surfaces disposed'within the disengaging space above a uidized bed have not been found practical for arresting the reaction of unreacted gases carrying powdered catalyst f in suspension.

- Anobject of my invention is to provide effective and convenient means for controlling exothermic reactions as unreacted gases and suspended catalyst powders pass from reaction zones provided with suitable control means to zones not so provided.

A further object is to prevent the temperature of incompletely reacted gases carrying entrained catalyst from rising above a desired level because of a continuing exothermic reaction after they have left the main reaction zone.

Another object is to prevent degradation of the reaction products and/or catalyst from overheating by the heat generated by continuance of an exothermic reaction outside of the sphere of influence of the control means applied to the reactor.

A still further object is to facilitate the carrying on of gaseous exothermic reactions involving fluidized catalysts in a step-wise manner.

Still another object is to simplify the removal of ventrained catalyst powder from incompletely reacted gases emerging from a controlled reaction zone, withoutl resorting to expensive and cumbersomecooling devices to avoid undesired effects from a continuing exothermic reaction.

These and additional yobjects of my invention will become apparent from the description which follows.

In accordance with my invention, the control of-an exothermic reaction of a'gaseous suspension comprising `incompletely "reacted gases' or vapors and powdered catalyst is achieved by introducing into the suspension anagent which diminishes or even nullies the activity of the jcatalyst. Through proper' vselection ofagent and regulation of amount v-usecLth'e exothermic reaction may be restrained or' completely blocked, as desired. While the process of my invention is applicable to any exothermic system wherein unreacted gases carrying catalyst particles pass from a reaction zone having suitable controF-means to a zone lacking adequate controls, it is particularly valuable in fluidized catalyst operations.

The agent injected into the gaseous suspension may be in solid, liquid or gaseous form so long as under the conditions of use itexerts a repressive eiect on the activity of the catalyst. However, for simplicity and rapidity of mixing the agent with the gaseous suspension, it is generally desirable to add a gaseous agent or one that has been pre-vaporized. The catalyst repression agent may be any material known to act as a poison toward the particular catalyst in use and, preferably, is of the type which is readily dispelled when it is desired to have the catalyst in a regenerated condition again.

The accompanying drawings, in which similar parts are designated by like reference characters, diagrammatically illustrate in vertical section the upper portion of four forms of iluidizing reactor suitable for carrying out the process of my invention. It should be understood that these illustrations are only by way of example and that many other modifications and alternative arrangements i'all within the scope of the invention.

Figure 1 shows the upper part of a reactor for carrying out fluidized catalyst processes in which means are provided for introducing a gaseous or liquid agent at a plurality of points and in which entrained catalyst is removed from the efiiuent gases by means of a replaceable filter element.

Figure 2 shows the upper part of a reactor having two lter elements which, alternately, are employed to separate the catalyst from the gaseous effluents and to inject the catalyst repressor.

Figure 3 shows a modification of the apparatus of Figure 2 to permit the removal of the separated catalyst from the reactor.

Figure 4 shows the upper part of a reactor in which a cyclone separates entrained catalyst from the eliluent gases, while a suitable agent is injected into the gaseous suspension to control any continuing exothermic reaction.

Referring to Figure 1, the reference character I denotes a vertical reaction chamber adapted to carrying out reactions in the presence of a fluidized catalyst. 'Ihe shape of the reactor is not critical and various forms may be employed. The lower part, which may be provided with the usual gas feed pipes, catalyst draw-off pipes, etc.,

has been omitted for the sake of simplicity.'

Within reactor I a mass 2 of nely divided catalyst is maintained in a turbulent state by the upward flow of gaseous reactants which have a velocity not quite suilicient to overcome all the gravitational forces on the catalyst particles, with the result that a relatively dense but uidized bed of catalyst resides in thelower portion of reactor I. This dense catalyst mass appears to act as a boiling liquid and has a pseudo-liquid level 3 which is the region where the reaction gases separate themselves from the bulk of the catalyst mass. Because of the tendency for some of the catalyst particles to become entrained in the emerging gases, a cloud or relatively light dispersion of catalyst is formed above level 3; settling zone 4 is provided to assist in disengaging the gases from the catalyst particles. Disposed within catalyst mass 2 is a cooling coil 5 through which water or other suitable cooling medium is passed. 'I'he means of controlling the temperathrough purge line 23 or 23A, respectively. Valves 23 and 23A when the respective casings to which ture within the dense bed of uidized catalyst forms no part of the invention, however, and any other suitable means may be employed, such as circulating the uidized catalyst through an external cooler.

A lter element E, e. g., porous alumina refractory, is positioned within the outlet of reactor I and may be conveniently fastened by means of clamping ring 8. Suitable gaskets I are placed on both sides of the anged edge of filter 6 and clamping ring 8 is tightened by turning down nuts I0 on bolts 9. Gases passing through filter 6 enter outlet dome Il, which may be secured to the reactor I by welding.

In the vicinity of t e pseudo-liquid level 3 of the fluidized catalystl ass 2 means are provided for introducing an a 'ent which represses or stops the catalytic reaction. The agent may be introduced through line I2 into a circular manifold I3 from which it discharges by way of branch lines Il and nozzles IIS into the catalyst disengaging or settling zone 4. In this manner, any continuing exothermic reaction within zone 4 and especially on the surface of filter 6 where the catalyst powder tends to build up an appreciable layer is diminished or checked completely, as desired.

Figure 2 shows a system which is adapted for introducing the catalyst repressor and simultaneously usingr it as the gas for blowing baci; catalyst collecting upon the lter. For this purpose, reactor l is provided with two outlets II and IIA, having illters 6 and 6A, respectively. Outlet members Il and IIA are connected to a common manifold I6 by way of valves I9 and HSA, respectively, which can be turned so that each outlet member communicates either with discharge line I8 or with one of the inlet lines Il and I IA through which the repressing agent is introduced. This alternating arrangement obviates special means for introducing the repressing agent, such as shown in Figure 1, and avoids interruptions in the withdrawal of reaction gases caused by periodic blow-backs to clear the filters.

In operation the two valves I9 and ISA are turned alternatingly with each other to put their respective outlet domes I I and I IA into communication with discharge line I 8 and inlet line I1 or I1A,`respectively. Thus, with the valve setting shown in Figure 2, while product gases from the reactor are passing out through filter 6, outlet II, valve I9, manifold I6 and discharge line I8, the catalyst repressing agent is flowing through inlet line I1A, valve I9A, outlet I IA and lter 6A into disengaging zone 4. When it is desired to remove the catalyst layer which has been formed on filter 5, the settings of valves I9 and ISA are reversed so that the repressing agent is charged into the reactor from line I1 through lter 6 while the eilluent gases pass out of the reactor through filter 6A and discharge line I 8.

In Figure 3, the lters 6 and 6A are enclosed in casings 20 and 20A, respectively, equipped with dampers or valves 2I and 2IA which are controlled by valve stems 22 and 22A. The operation of these valves is synchronized with that of valves I9 and I 9A to permit reaction products to enter the unit which has been placed in communication with discharge line I8 and to close the other unit during the blow-back period. With this arrangement, the catalyst removed from the surface of :filter 6 or iA passesout of the reactor 28 and 28A are also provided to close purge lines Figure 1.

. bons.

s 8 they are attached are in commlmication with settling zone 4. The medium used for removing catalyst from the lters may be either the repressing agent or any other desired iuidgaseous or even liquid. The catalyst thus withdrawn from the reactor may beput through a regeneraf tion step before reinjection into the reaction zone.

The device for introducing the catalyst repressor in the present apparatus is the same circular manifold and nozzle arrangement as shown in Itr is understood that the catalyst purged fromthe filters maybe returned to the reactor by the usual methods. e. g., by suspension in the feed stream of reactant gases. With the valve setting shown in Figure 3, the repressor discharges from nozzles I and mixes with the reaction gases in settling zone 4. The mixed gases pass through open damper 2l and lter 6 separates entrained catalyst powder. The ltered gases leave through dischargeiline I8. At the same time, a purging medium, e. g., hydrogen, nitrogen or steam, entering through inlet I'IA dislodges any catalyst powder deposited on filter 6A and carries it out of casing r20A by way of purge line 2SA. Valve 28A is open while valve 28 is closed. By changing the valve setting, filter 6 may be purged and filter 6A used to filter the reaction gases.

In Figure 4 a cyclone separator 24 is used to separate entrained cataylst from gases leaving reactor I. Separator 24 has an inlet 25, a gas outlet 26 and a standpipe 2I for conducting the separated catalyst powder back into the fluidized catalyst bed 2. In this case the catalyst repressor may be simply injected into cyclone inlet 25 through nozzle I5, although it may be fed into settling zone 4, as shown in Figures 1 and 3, particularly in cases of highly exothermic reactions which tend to continue even when there is a relatively low concentration of suspended catalyst in zone 4.` This system may be adapted to permit external regeneration of catalyst by having standpipe 21 discharge into an external hopper or regenerator, or a conventional arrangement of external cyclones, hoppers, regenerator, etc., may be employed, with introduction of the catalyst repressing agent into the settling zone or directly into the cyclone separator as the case may require.

As a specic example of the use of my invention, I maintain in reactor I a fluidized bed of powdered iron catalyst while passing therethrough synthesis gas comprising n hydrogen and carbon monoxide under conditions of temperature and pressure suitable for theformation of hydrocarthe iluidized mass 2 by a cooler 5 or by circulating the fluidized catalyst through an external cooling unit. Ammonia is introduced through line I 2 in amounts equal to about 5 to 15% by volume of the unreacted carbon monoxide in the gas emergling from the bed of uidized catalyst. Larger amounts of this catalyst repressor are not harmful. Reactivation of the catalyst which has been exposed to the ammonia is not necessary since the repression or poisoninglof the.` catalyst is of a transient nature. Therefore, the catalyst may be permitted to fall backl into the fiuidized catalyst bed after its separation from the eluent gases without detriment to the reaction. The reactor arrangements shown in Figures l, 2 and 4 are suitable forthis example. The ammonia leaving reactor I in admixture with the reaction gases is contained predominantly in the aqueous phase which is forme'd when the reaction products are condensed, thus facilitating its separation. Any

Excess heat of reaction is removed from'v Several schemes have been-,proposed to control exothermic reactions, which depend upon the introduction of substances other than the reactants into the systemto exert some physical effect, e. g., dilution oi he reactants or heat abstraction through vapo 'ization of an added substance. Such` method depending upon a mere physical effect suffer rom the inherent disadvantage hat a relat vely large amount of the material nust be added, necessitating the use of larger equ pment and complicating the fractionation and recovery cf the reaction products.

In contrast to such prior proposals, my invention utilizes an agent which exerts a negative catalytic or catalyst-poisoning action. While some might argue. that my catalyst repressors function physically as much as chemically, in the final analysis it is to be noted that a catalyst repressor for the purposes of my invention is an agent which permits control of an exothermic reaction to a greater degree than is attributable to mere dilution and heat absorption eiects. When the repressing agent has only a transient effect upon the catalyst, regeneration of the portion of the catalyst which has been exposed to this agent is not necessary and the catalyst may be permitted to return directly to the main reaction zone. When the repressor is of the type ofa persistent poison, it is usually desirable to remove the contaminated portion of the catalyst for regeneration outside the reactor, in order to prevent the main body of the catalyst from becoming gradually deactivated or the accumulation of an appreciable concentration of repressor Within the reaction zone. tion, however, that some substances which exert a repressing action at certain concentrations are substantially without eiect or are even benecial to the catalytic reaction when present in smaller concentrations. It is apparent that Wherethe amount of the agent introduced into the main 5o body of the reaction by the contaminated catalyst is below a harmful level the removal and regenwrgation of this catalyst outside the reactor may not bfnecessary.l Ammonia may be considered a catalyst repressor of this type. In the synthesis 55 of hydrocarbons, when ammonia present in amounts equal to about 5 to 15% by volume of the carbon monoxide, the catalytic hydrogenation of carbon monoxide is measurably repressed; on the other hand, it is reported thattraces of ammonia enhance catalytic activity in the synthesis ofA hydrocarbons.

Through my invention I have beenenabled to devise a new processy for the catalytic hydrogenation or carbon monoxide involving stepwise operation in two or more fluidizing reactors and separation of reaction products, particularly water, from the unreacted components between steps. By this process, the fluidizing catalyst technique is applied to the hydrogenation of carbon monox- 70` ide under vary favorable conditions since it is possible to withdraw reaction'fproducts one or more times in the course of the reaction and thus minimize the undesirable eiects of increasing concentration of reaction" products in the reacting gases. Removal of the Water of `reaction between It is interesting in this connecn steps apparently is conducive to the maintenance of higher catalytic activity. At the same time, these advantages are realized without encountering the difficulties of separating entrained catalyst powder from gases comprising exothermically reactive components. The process,-for example, may be employed to synthesize hydrocarbons in the presence of comminuted catalysts prepared from metals of the iron group. Two or three fiuidizing reactors, preferably of decreasing capacity, are arranged serially with provisions for the withdrawal of reaction products between reactors. At these withdrawal points, there is a preceding separation of entrained catalyst from the reaction gases, conducted in the presence of a catalyst repressor, e. g., ammonia, in accordance with my invention. Generally, in such stepwise operation, ya to of the Icarbon monoxide charge will be converted in the first reactor, the remainder being found in the eilluent gases and converted in subsequent reaction steps.

The purpose of using a catalyst repressor is not limited to facilitating stepwise operation. The process of my invention is equally applicable. for instance, to catalytic oxidations in which it is desired to use an excess of oxidizing gas to attain more nearly complete conversion of an organic compound to an oxygenated product without producing carbon dioxide and the like because of over-oxidation. Such over-oxidation is certain to occur in a iluidizing system unless the catalytic reaction is controlled through the addition of a catalyst repressor in the region in which the separation of reaction gases and cata lyst lpowder is elected. Similarly, my process is of use in the selective hydrogenation of certain components of mixtures of olenic compounds, the objective being to prevent excess hydrogen from adding to the olefms that are desired unaltered.

Those skilled in the art are aware that there are many substances known to act as catalyst repressors or poisons; the selection of these substances for the purposes of my invention will of course depend upon the particular reaction and catalyst which are to be controlled, on the reactivity of the substance with the gaseous reactants or products, on the ease of regenerating the catalyst, on the facility with which the substance may be separated from the reaction gases, etc.

By way of example, the following combinations of reactants, catalysts and poisons are cited. In the vapor-phase catalytic oxidation of aromatic compounds like toluene and naphthalene to benzoic acid and phthalic anhydride, respectively. in the presence of catalysts such as vanadium and chromium oxides, suitable repressors are lead tetraethyl, iron pentacarbonyl and iodine vapor.

Similarly, the oxidation of methanol to formalde-r hyde with a catalyst of the molybdenum oxide type may be controlled by additions of chlorineor sulfur-containing compounds. Reactions catalyzed by platinum may be repressed by the introduction of carbon monoxide. The destructive hydrogenation of mineral oils in the presence of a catalyst comprising molybdenum sulde and zinc oxide is brought under control by using steam or oxygen as repressor. Besides ammonia previously mentioned hereinabove. the catalytic synthesis of organic compounds from hydrogen and carbon monoxide with .the aid of an iron, nickel or cobalt catalyst may be controlled by sulfur compounds, e. g., hydrogen sulilde and thiophene.

When ammonia is used according to the invention in the synthesis of hydrocarbons or other catalytic reactions, a special advantage obtainsv in cases where electrostatic precipitation methods are employed for separating entrained catalyst from the eilluent gases, since it is known that such separations are greatly facilitated by the presence of ammonia.

The invention is not predicated on the use of special temperatures, pressures, velocities, contact times, catalyst particle sizes, etc., and, accord- 4, ingly, no attempt is made to deilne the operable ranges for such vprocess factors. Furthermore, these data vary with the reactions and are known to those skilled in the arts.

It is apparent that numerous modiilcations may be made in the speciilc arrangements and procedures described without departing from the scope of the invention.

I claim:

1. In fluidized catalyst dense-phase processes involving exothermic reactions, the method oi separating entrained catalyst particles from incompletely-reacted gases or vapors', which comprises ilowing said gases or vapors into a zone comprising a plurality of ltering portions, illtering said gases or vapors by passage through at least one of said filtering portions, and simultaneously introducing into said zone by passage in the reverse direction through at least one other of said filtering portions a substance which chemically represses the activity of said entrained catalyst particles.

2. The method of claim 1 wherein the catalyst comprises an element of the iron group and the incompletely reacted gases comprise hydrogen and carbon monoxide.

3. The method of claim 2 stance is ammonia.

4. The stepwise process of synthesizing hydrocarbons from hydrogen and carbon monoxide by contact with particulate catalyst comprising an element of the iron group in a fluidized state, which comprises introducing said gaseous reactants into a fluidized bed of said catalyst, effecting reaction of only a portion of said gaseous reactants while passing through said iluidized Ibed, withdrawing from said iluidized bed a gaseous stream containing a portion of said gaseous reactants, the products of reaction and entrained wherein the subparticles of said catalyst, adding to said gaseous stream an amount of catalyst poison which chemically represses4 the activity of said catalyst but which is insufcient to eiect substantial cooling by heat absorption, separating said entrained particles from said gaseous stream, removing at least a portion of said products of reaction and said catalyst poison from said gaseous stream, thereafter introducing said gaseous stream into a second fluidized bed oi said catalyst, and effect-r lower portion of a vertically elongate chamberv and emerges from said dense phase in the upperassenti in each of said housings to provide communication between said elongate chamber and the interior of each of said housings, an outlet pipe communicating with the interior of each of said housings, a lter in each of said housings interposed between the valved opening and the outlet pipe of each of -said housings, a withdrawal pipe communicating with each outlet pipe for withdrawing filtered gas from each housing, a feed pipe communicating with each outlet pipe for introducing a blow-back gas into each housing by passage through the iilter in said housing, and a discharge pipe for the blow-back gas communicating with the portion of the interior of each housing which portion lies between the' valved opening and the iilter in said housing.

8. In iiuidized catalyst dense-phase processes involving the synthesis of hydrocarbons from hydrogen' and carbon monoxide by contact with particulate catalyst comprising an elementvof the iron group, the method of separating entrained catalyst particles from incompletely reacted gases, which comprises simultaneously flowing said gases into a zone comprising a plurality of ltering portions, introducing into said gases flowing into said zone an amount of catalyst poison which chemically represses the activity of said entrained catalyst but which is insufficient to eileot substantial cooling by heat absorption, ltering said gases containing said catalyst poison by passage through at least one ot said illteringportions to separate therefrom said entrained catalyst without an undesirable temperature increase, and removing catalyst accumulated in at least one other of said filtering portions which has pre' viously been separating said entrained catalyst from said gases containing said catalyst poison.

9. In the exothermic synthesis of hydrocarbons, oxygenated hydrocarbons and mixtures thereof from hydrogen and carbon monoxide in lo the presence of a iluidized dense bed of catalyst particles comprising an element of the iron group wherein a gasiform stream emerges from said bed and contains unreacted hydrogen -and carbon monoxide and entrained catalyst particles. the improvement which comprises injecting into said gasiform stream as it emerges from said bed y an amount of catalyst poison which chemically represses the activity of said catalyst particles but which is insumcient to effect substantial cooling by heat absorption, and separating said entrained catalyst particles from .said gasiform stream containing the injected catalyst poison without an undesirable temperature increase.

10. The synthesis process of claim 9 wherein the catalyst poison is ammonia.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,784,339 Clasen et al Dec. 9. 1930 1,806,513 Straus-Scharinal May 19, 1931 1,845,058 Pier Feb. 16, 1932 2,291,510 'I'homas et al July 28, 1942 2,347,682 Gunness May 2, 1944 2,356,717 .Williams Aug. 22, 1944 2,391,534 Yerrick et al Dec. 25, 1945 2,393,778 Hull Jan. 29, 1946 2,394,651 Alther Feb. 12, 1940 2,409,751 Gerhold .et al Oct. 22, 1946 2,417,164 Huber Mar. 11, 1947 2,429,751 Gohr et al. Oct. 28, 1947 2,448,279 Rubin Aug. 31,1948

FOREIGN PATENTS Number Country Date 444,936 Great Britain Mar. 31, 1930 

9. IN THE EXOTHERMIC SYNTHESIS OF HYDROCARBONS, OXYGENATED HYDROCARBONS AND MIXTURES THEREOF FROM HYDROGEN AND CARBON MONOXIDE IN THE PRESENCE OF A FLUIDIZED DENSE BED OF CATALYST PARTICLES COMPRISING AN ELEMENT OF THE IRON GROUP WHEREIN A GASIFORM STREAM EMERGES FROM SAID BED AND CONTAINS UNREACTED HYDROGEN AND CARBON MONOXIDE AND ENTRAINED CATALYST PARTICLES, THE IMPROVEMENT WHICH COMPRISES INJECTING INTO SAID GASIFORM STREAM AS IT EMERGES FROM SAID BED 